KR20170021772A - Reference electrode - Google Patents

Abstract

The present invention is intended to maintain the conduction between the internal liquid and the liquid to be measured and measure the potential of the liquid to be measured in the liquid portion of the comparative electrode even when bubbles are mixed in the liquid. (40) arranged in the second inner liquid chamber (36) such that the second inner liquid (15) and the measurement liquid (9) to be measured come into contact with each other, and a second inner liquid chamber 2 body 42 and an inner electrode R disposed in the second inner liquid chamber 36. The liquid container 40 includes a conductive member 41 formed of a porous or fibrous member, (45) adjacent to the supporting member (41).

Description

[0001] REFERENCE ELECTRODE [

The present invention relates to a comparative electrode used as an electrochemical measuring device such as a pH measuring device.

In the electrochemical measuring apparatus using the glass electrode method including the pH measuring apparatus, a measuring electrode and a comparison electrode are provided. For example, as shown in Patent Document 1, in the internal liquid chamber of the comparative electrode, the internal electrode is arranged so as to extend upward from the lower end, and the upper electrode A flow path through which the liquid flows horizontally is formed, and a partition wall is provided between the flow path and the internal liquid chamber. In this partition wall, there is provided a columnar columnar portion extending vertically, and an upper portion of the columnar portion is opened. Since this opening is arranged so as to be in parallel with the flow of the measurement liquid, in this case, if the measurement liquid contains bubbles, the bubbles flowing in the flow path may hang over the entire opening. In such a case, the bubbles block the conduction of the liquid to be measured and the liquid in the liquid-filled portion, and the potential of the liquid to be measured can not be measured or becomes unstable.

In the case where a fiber-like conduction member such as cloth is provided on the entire liquid portion, bubbles may remain on the liquid. In this case, too, the bubbles cause the measurement liquid in the liquid- The conduction of the internal liquid is interrupted and the above problem may occur.

: Japanese public utility model publication 59-183655

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-described problems, and it is an object of the present invention to provide an apparatus and a method for measuring the potential of a liquid to be measured, The main task is to be able to do.

That is, the comparison electrode according to the present invention comprises: an inner liquid chamber containing an inner liquid; a body having a liquid lock portion disposed in the inner liquid chamber so that the inner liquid and the measurement liquid to be measured come into contact with each other; And the liquid crystal portion is formed of a conductive member formed of a porous or fibrous member and an opening adjacent to the conductive member.

With this configuration, since the liquid portion is formed by the conductive member and the opening adjacent to the conductive member, when the liquid to be measured flows into the liquid-tight portion, the fluidic resistance tends to flow into the opening side having smaller fluid resistance than the conductive member, When the liquid contains bubbles, the bubbles tend to stay on the opening side along the flow.

Therefore, the conductivity-imparting member is not covered by the bubble, the measurement liquid penetrates into the porous material or the fibers of the conduction member, and the conduction of the measurement liquid and the internal liquid is maintained by the contact with the internal liquid. .

If the size of the opening is made larger than the size of the fine hole of the conductive member, the effect of the present invention can be surely provided.

In order to prevent the bubbles from staying further at the end of the conducting member which is in contact with the measuring solution due to the bubbles contained in the measuring solution, the end portion of the conducting member, which is in contact with the measuring solution, Or to protrude from the opening toward the measurement liquid side. Particularly, in the case of the configuration in which the opening is opened by the flow path through which the measurement liquid flows, if the conduction member protrudes toward the measurement solution side from the opening, the flow path of the end portion of the conduction member is narrowed, The flow rate can be increased. This makes it difficult for the bubbles to remain at the ends of the interconnecting members. At this time, it is preferable that the conductive member protrudes to the center of the cross-section of the flow passage (in the case of the circular passage in the section, the center of the circle).

In addition, even when the entire bubble is present in the entirety of the liquid-tight portion, it is preferable that the conduction member is provided so as to extend in the direction of the inner pole so that the inner liquid can penetrate into the conduction-member.

As a specific kind of the arrangement of the openings, it is preferable that the opening is arranged on the downstream side of the flow of the measurement liquid in the case where the measurement liquid accommodating portion containing the measurement liquid flows in one direction .

As a specific kind of arrangement of the interconnecting member in the inner liquid chamber, the measurement liquid containing portion is located above the inner liquid chamber, and is located above the upper end of the inner electrode, The inner liquid chamber is formed such that the sectional area of the liquid chamber becomes smaller than the sectional area below the position at the predetermined distance, and the conductive member is arranged between the above-mentioned predetermined distance from the above-mentioned liquid- .

And a connection pipe for connecting the internal liquid chamber and the measurement liquid containing portion, wherein the connection pipe includes a bottom pipe portion and a bottom pipe portion extending upward from one end of the bottom pipe portion, And a second communicating pipe portion extending upward from the other end of the bottom pipe portion and communicating with the inner liquid chamber, or the second communicating pipe portion communicating with the inner liquid chamber, A second communicating pipe portion extending downward from the other end of the upper pipe portion and communicating with the inner liquid chamber, and a second communicating pipe portion extending downward from the other end of the upper pipe portion and communicating with the inner liquid chamber, .

When the specific gravity of the liquid to be measured is larger than that of the liquid, if the liquid is provided below the vertical direction of the liquid holding portion, the liquid under test is pushed downward and flows into the connecting pipe from the liquid holding portion. However, the connection pipe may include a first communicating pipe portion extending upwardly from one end of the bottom pipe portion and the bottom pipe portion and communicating with the measurement liquid accommodating portion, and a second communicating pipe portion extending upward from the other end of the bottom pipe portion, It is possible to prevent the inflow of the measurement liquid into the inner liquid chamber and prevent the inner liquid contained in the inner liquid chamber from being corroded by the measurement liquid Can be prevented.

When the specific gravity of the liquid to be measured is smaller than the internal liquid, if the connection pipe is provided above the vertical direction of the liquid holding portion, the liquid to be measured pushes up the liquid and flows into the connection pipe from the liquid holding portion. However, it is preferable that the connection pipe includes a first communicating pipe portion extending downward from the one end of the upper pipe portion and the upper pipe portion and communicating with the measurement liquid containing portion, and a second communicating pipe portion extending downward from the other end of the bottom pipe portion, Since the second communicating pipe portion is provided, the inflow of the measurement liquid from the upper pipe portion is stopped, the measurement liquid is prevented from intruding into the inner liquid chamber, and the inner electrode accommodated in the inner liquid chamber is prevented from being corroded by the measurement liquid .

Therefore, in the comparative electrode of the present invention, it is possible to prevent the inner electrode from being corroded regardless of the specific gravity of the liquid to be measured.

And the connection pipe is connected below the vertical direction of the measurement liquid containing portion.

With this configuration, when the calibration is performed, the calibration liquid having a specific gravity smaller than that of the internal liquid is prevented from flowing into the connection pipe from the measurement liquid pipe, and corrosion of the internal electrode by the calibration liquid can be prevented.

And a liquid retaining member provided inside the connection pipe, wherein one end of the liquid retaining member is provided in contact with the conduction member and the other end is provided in the inner liquid chamber.

With this configuration, the measurement liquid or the internal liquid penetrates into the liquefier member, and the contact state of the measurement liquid and the internal liquid is maintained, so that the conduction of the measurement liquid and the internal liquid is maintained, and the potential measurement of the measurement liquid can be stably performed. As a concrete embodiment, it is conceivable that the liquefier member is a hollow fiber made of a material having chemical resistance (for example).

According to the present invention configured as described above, since the conducting member and the opening are formed in the liquid-tight portion, when the measured liquid flows into the liquid-tight portion, the fluidic resistance tends to flow into the opening with lower fluid resistance than the conducting member, The bubbles tend to stay on the opening side along the flow.

Therefore, the conducting member is not covered by the bubble, the measuring liquid penetrates into the porous material or the fibers of the conducting member, and the conducting liquid contacts with the inner liquid to maintain conduction between the measuring liquid and the inner liquid. .

1 is an overall schematic diagram of a measurement system according to a first embodiment of the present invention.
2 is a schematic view of an electrode device in the above embodiment.
3 is a partially enlarged view of the comparative electrode in the above embodiment.
Fig. 4 is a schematic view of the opening of the comparative electrode in the above-described embodiment. Fig.
Fig. 5 is a schematic diagram showing a pH measurement procedure in the above embodiment. Fig.
6 is a schematic view of an electrode device in another embodiment.
7 is a partially enlarged view of an electrode device in another embodiment.
8 is a schematic view of an electrode device in another embodiment.
9 is a perspective view of a comparison electrode in the second embodiment.
10 is a plan view of a comparison electrode in the second embodiment.
11 is a schematic view of a comparison electrode in the third embodiment.
12 is a schematic view of a comparison electrode in the fourth embodiment.
13 is a schematic view of a comparison electrode in the fifth embodiment.

≪ First Embodiment >

Hereinafter, a first embodiment of the present invention will be described with reference to the drawings.

Fig. 1 shows a measuring system 100 according to the present embodiment.

The measurement system 100 measures the hydrogen ion concentration and the like of a chemical solution used in a semiconductor manufacturing process such as cleaning of a wiring process, Cu plating solution, CMP (chemical mechanical polishing), etc. An electrode device 7 for measuring the pH of the measurement liquid 9 and a measurement liquid flow mechanism 3 for circulating the measurement liquid 9 through the electrode device 7, The electrode device 7 is provided with an internal liquid replenishing mechanism 5 for replenishing an internal liquid such as a KCl solution (which is the internal liquid of the comparison electrode described in claim 1, hereinafter referred to as " second internal liquid "), And an information processing and control mechanism 19 connected to the measurement liquid flow mechanism 3 and the internal liquid replenishing mechanism 5 and receiving measurement data and command signals therebetween. On the other hand, the measurement system 100 can measure ionic concentrations such as sodium and potassium, and gas concentrations (pCO2, pO2, etc.) of carbon dioxide and oxygen other than hydrogen ions.

As shown in Fig. 2, the electrode device 7 is provided with a measuring electrode 4, a comparison electrode 6, and a prime body 23 for accommodating them.

The measuring electrode 4 includes a first body 54 having a first inner liquid chamber 52 in which a predetermined inner liquid such as a pH buffer solution (hereinafter referred to as a "first inner liquid") is contained, And an inner pole (M) attached so as to extend upward from the first inner liquid chamber (52) from the bottom of the first body (54).

The first body 54 is formed of a material such as PVC (polyvinyl chloride), PP (polypropylene), PVDF (polyvinylidene fluoride) or the like. When the upper surface of the first body 54 is extended to cover the upper surface, And a lid body 54b for closing the lower opening of the main member. The first inner liquid chamber 52 formed in the first body 54 has a predetermined cross-sectional shape (for example, a cylindrical shape) from the lower end to a predetermined height, and only the upper end thereof is thinner The shape of the mold is reduced.

The inner electrode M is made of, for example, a silver / silver chloride electrode. The inner electrode M is attached to the lid 54b so that the lower end of the inner electrode M passes through the lid 54b, To be stretched upward. A contact is formed at the lower end of the inner pole M so that the current (voltage) signal can be taken out to the outside. The lower end of the internal electrode M is not limited to being extended from the lid 54b and may be inclined such that the first internal liquid chamber 52 is extended upward from the side surface of the main member 54a, For example, an L-shaped configuration.

Further, in this embodiment, the electrode device 7 is provided with the tube 58 through which the measurement liquid 9 flows.

This tubular body 58 is entirely formed of a response glass responsive to hydrogen ions, and forms a first flow path 62 through which the measurement liquid flows. This response glass is a predetermined amount of scandium. The shape of the tubular body 58 is such that the length thereof is sufficiently long with respect to the capillary shape, that is, with respect to the inner diameter. For example, the inner diameter of the tube 58 is about 0.1 mm to 2 mm, preferably about 0.5 mm to 1 mm I will go. The thickness of the tubular body 58 is about 0.1 mm to about 1 mm, preferably about 0.2 mm, and if it is such a thickness, a responsive glass having good responsiveness is obtained. The outside diameter is preferably about 0.3 mm to about 4 mm, and preferably about 1 mm to about 2 mm.

The tubular body 58 horizontally passes through the upper end of the first body 54 and is arranged so as to be immersed in the first inner liquid 50 of the first inner liquid chamber 52. More specifically, the tubular body 58 is located above the upper end of the inner pole M and is arranged to pass through a certain cross-sectional shape portion of the first inner liquid chamber 52.

On the other hand, the tubular body 58 may use a response glass for a part of the tubular body 58 which is immersed in the first inner liquid 50.

Next, the comparative electrode 6 will be described with reference to Fig.

The comparison electrode 6 includes a second body 42 having an inner liquid chamber (the inner liquid chamber of the comparison electrode described in claim 1, hereinafter referred to as "second inner liquid chamber") in which the second inner liquid 15 is accommodated, (R) attached to extend from the lower part of the second body (42) upward to the second inner liquid chamber (36), and an inner electrode And a replenishing port (17) formed in the first inner liquid chamber (42) for replenishing the second inner liquid (15) communicating with the second inner liquid chamber (36).

The second body 42 is further provided with a flow path in which the measurement liquid 9 flows horizontally above the second body 42 (the measurement liquid containing portion of the comparison electrode according to claim 5, And the liquid immersion part 40 disposed in the second internal liquid chamber 36 so that the second internal liquid 15 and the measurement liquid 9 come into contact with each other. The liquid portion 40 is formed of a conductive member 41 formed of a porous or fibrous member and an opening 45 adjacent to the conductive member 41.

Like the first body 54 of the measuring electrode 4, the second body 42 is formed of a material such as PVC. When the upper surface of the second body 42 is vertically elongated and the upper surface of the second body 42 is closed, Shaped main member 42a and a lid member 42b for closing the lower opening of the main member.

The second inner liquid chamber 36 formed in the second body 42 has a cylindrical body which is formed so as to extend upward from the lower portion of the second body 42 and is located above the upper end of the inner pole R And a sectional area from the upper end 43 of the second inner liquid chamber 36 to a predetermined distance L1 downward is formed to be smaller than the sectional area below the position at the predetermined distance L1 have. The capacity of the second inner liquid chamber 36 from the upper end 43 of the second inner liquid chamber 36 to the predetermined distance L1 is smaller than the amount of the second inner liquid 15 replenished from the replenishing port 17 Is set to be smaller. The upper end portion 43 of the second inner liquid chamber 36 is connected to the second flow path 64. On the other hand, in this embodiment, the upper end portion 43 of the second inner liquid chamber has a conical shape in which the sectional shape is reduced toward the upper side. However, the shape is not limited to this, May be in contact with the second inner liquid 15.

On the other hand, between the upper end 43 of the second inner liquid chamber 36 and the predetermined distance L1, the cross-sectional area thereof may be constant or vary, and up to the predetermined distance L1 Sectional area smaller than the cross-sectional area of the lower-side portion. The cross-sectional area of the portion lower than the position at the predetermined distance L1 may be either constant or varied.

A second flow path 64 through which the measurement liquid 9 flows is formed above the second body 42. The second flow path (64) is formed horizontally on the upper end of the second body (42).

A liquid-storing portion 40 to be described later is formed so that the measuring liquid 9 flowing through the second flow path 64 and the second inner liquid 15 come into contact with each other. In this embodiment, the connection hole 49 formed below the inner peripheral surface of the second flow path 64 and the upper end 43 of the second inner liquid chamber 36 are connected. Although the connection hole 49 is formed to have a substantially circular shape in the present embodiment, the connection hole 49 is not limited to this, and may be an elliptical shape or a rectangular shape.

On the other hand, although the second flow path 64 is formed above the second body 42, the second flow path 64 is not limited to this but may be formed below the second body 42. [ In this case, the second flow path 64 is connected to the lower end of the second inner liquid chamber 36 via the connection hole 49.

In this embodiment, the measurement liquid accommodation portion is the flow path through which the measurement liquid 9 flows. However, the measurement liquid accommodation portion is not limited to the flow path, and may be a container in which the measurement liquid 9 is stored. The second inner liquid 15 may be brought into contact with the liquid 9.

Next, the liquid-tight portion 40 will be described with reference to Figs. 3 and 4. Fig. This liquid-filled portion 40 is formed by the interconnecting member 41 and the opening 45 adjacent to the interconnecting member 41. [ The reason why the opening 45 is adjacent to the interconnecting member 41 is that the interconnecting member 41 and the opening 45 are arranged so as to be in contact with each other, The bubble 47 that is close to the liquid crystal part 40 does not cover the interconnecting member 41 and can stay in the opening 45 even if there is something other than the interconnecting member 41 between the interconnecting member 41 and the opening 45. [ And the opening 45 is disposed at a position as close as possible. This close position is more preferably a case where the bubbles 47 are arranged at a smaller interval than the bubbles 47 contained in the measurement liquid 9. [

The conduction member 41 is formed of a porous member having a plurality of fine holes, such as ceramic, polyethylene, Teflon (registered trademark), and the like, and the measuring liquid 9 flowing through the second flow path Respectively. The conductive member 41 is rod-shaped or string-shaped so as to extend in the direction of the inner pole R and is located above the upper end of the inner pole R, Is disposed between the upper end portion (43) and the predetermined distance (L1) of the second inner liquid chamber (36). That is, the lower end of the interconnecting member 41 may be at any position between the upper end 43 and the predetermined distance L1 of the second inner liquid chamber 36, It may be above the top.

On the other hand, if the interconnecting member 41 is rod-shaped, the lower end may be fixed to the inner wall surface of the second inner liquid chamber 36 with an adhesive or the like, or the upper end may be fixed to the second inner liquid chamber 36 Or the intermediate portion may be adhered to the inner wall surface of the second inner liquid chamber 36. In this case, The upper end portion of the conductive member 41 is adhered and fixed to the upper end portion 43 of the second inner liquid chamber 36 with an adhesive or the like and the middle portion thereof is fixed to the second inner liquid chamber 36 As shown in Fig.

On the other hand, when the interconnecting member 41 is a fibrous member, it is formed of, for example, chemical fibers and has a plurality of fine holes between the fibers.

In this embodiment, the conduction member 41 is disposed so as to be located on the upstream side of the flow of the measurement liquid 9, but the present invention is not limited to this, and the conduction member 41 may be disposed on the downstream side of the flow of the measurement liquid 9 Alternatively, the conductive member 41 may be arranged so that the opening 45 surrounds the conductive member 41 in a ring shape.

3 (a), the interconnecting member 41 is arranged so that the upper end thereof protrudes from the second flow path 64 more than the opening 45. As shown in Fig. In this embodiment, the upper end portion of the interconnecting member 41 has a shape tapering upward, and is disposed so as to protrude to the vicinity of the center in the radial direction of the second flow path 64. On the other hand, the shape of the upper end portion is not limited to this, but may be a rounded shape or a substantially planar shape.

3 (b), the interconnecting member 41 may be disposed so that the upper end thereof is substantially flush with the opening 45. In this case, the upper end portion of the interconnecting member 41 is roughly And has a planar shape. On the other hand, the shape of the upper end portion of the interconnecting member 41 is not limited to this. The upper end portion may have a thin and sharp shape as shown in Fig. 3 (a), or a rounded shape, And may be located on the same plane as the opening 45.

The upper end portion of the interconnecting member 41 may be disposed at a lower position than the opening 45 to the extent that the air bubbles do not stay in the upper end portion.

On the other hand, the position of the upper end portion of the interconnecting member 41 is preferable because it is easier to arrange the portion that protrudes than the opening 45, rather than being disposed on substantially the same plane as the opening 45 described above.

The opening 45 constituting the liquid container 40 is connected to the second internal liquid chamber 36 and the second flow path 64 and is arranged so as to have a width of dimension a . The dimension a means the length from the interconnecting member 41 to the periphery of the opening 45 in the opening 45. [ In the case where the opening 45 is formed in the ring shape around the interconnecting member 41, the dimension a is the length of the width of the ring shape.

The dimension (a) is set to be larger than the size of the fine holes of the interconnecting member (41). The fine holes may be of various shapes such as a substantially circular shape or a substantially rectangular shape. In general, surface tensions act on the bubbles to maintain the shape of the bubbles, so that the shape of the holes in which the bubbles are likely to stay includes a substantially circular shape, a shape close to it, or an elliptical shape. In addition, the smaller holes are less likely to stay in the bubbles. The dimension a is set so as to be larger than the diameter or the major diameter of the largest of the minute holes of the interconnecting member 41 in this shape. The air bubble 47 stays on the gap side of the branch, so that the air bubble can be prevented from covering the interconnecting member 41.

On the other hand, the dimension (a) is not limited to be set as described above. If the shape of the fine hole of the interconnecting member 41 is a round or a square, May be set to be larger than the maximum of the lengths of the diagonal lines. That is, the dimension a of the opening 45 may be set larger than the fine hole of the interconnecting member 41. By setting in this way, the bubble 47 remains on the gap side having the dimension (a).

The bubbles 47 contained in the measurement liquid 9 mean bubbles generated by pressure fluctuations and bubbles such as hydrogen peroxide in the measurement liquid 9 when the measurement liquid 9 flows through the flow path If it is easy to contain, it is the bubble caused by it.

The inner electrode R is made of, for example, a silver / silver chloride electrode. The inner electrode R is attached to the cover 42b such that the lower end of the inner electrode R passes through the cover 42b. It stands to be stretched upward. A contact is formed at the lower end of the inner electrode R so that the current (voltage) signal can be taken out to the outside. The inner electrode R is not limited to the case where the lower end of the inner electrode R is extended from the lid 42b and may be inclined such that the second inner liquid chamber 36 is extended upward from the side surface of the main member 42a, For example, an L-shaped configuration.

The replenishing opening 17 is provided at a position slightly lower than the upper end of the inner pole R in the present embodiment, but may be changed as appropriate. For example, The second inner liquid 15 may be disposed at a position where the second inner liquid 15 can be replenished from the bottom of the inner pole R or at the center or the upper side of the inner pole R. [

Next, the prime body 23 will be described with reference to Fig. The prime body 23 is formed of, for example, a rectangular box-shaped resin, metal or the like having an open top, and the measuring electrode 4 and the comparative electrode 6 are fitted to the prime element from above without rattling Loses.

The bottom plate of the prime mover 23 is provided with contact portions 88 and 89 which are in contact with lower ends of the inner pole M and the inner pole R, respectively.

An inlet hole 63 for introducing the measurement liquid 9 into the tube 58 flowing through the first flow path 62 is formed on one side plate of the prime mover 23 in contact with the measurement electrode 4, An outlet hole 65 is formed in the other side plate in contact with the comparison electrode 6 so that the measurement liquid 9 flowing through the second flow path 64 flows out. An inflow hole 67 for introducing the second inner liquid 15 into the replenishing port 17 is also formed in the other side plate.

As described above, the electrode device 7 is constituted by the measuring electrode 4, the comparing electrode 6 and the prime body 23, and the measuring electrode 4 and the comparing electrode 6 are connected to each other through the inlet hole 4, The replenishment port 17 and the inflow hole 67 are communicated with each other so as to communicate with the prime body 23 (23), the first flow path 62, the second flow path 64 and the outflow hole 65, . Here, the measuring electrode 4 and the comparing electrode 6 are fixed to each other by, for example, a not-shown screw or the like, whereby the first flow path 62 and the second flow path 64 And the measurement liquid 9 is not leaked therebetween. An O-ring or the like may be provided between the first flow path 62 and the second flow path 64 to improve the adhesion. The tube 58 of the measurement electrode 4 is fixed to the first body 54 through an adhesive or the like so that the first internal liquid 50 is held in the first internal And is not leaking from the liquid chamber 52.

Next, the measurement liquid flow mechanism 3 will be described with reference to Figs. 1 and 2. Fig.

The measurement liquid circulating mechanism 3 includes an inlet pipe 12a for introducing the measurement liquid 9 into the electrode device 7 and an outlet pipe 12a through which the measurement liquid 9 flowing through the electrode device 7 flows And a flow pump 10 arranged at a predetermined position of the inflow pipe 12a or the outflow pipe 12b for introducing and discharging the measurement liquid 9 thereinto.

The distal end of the inflow pipe 12a is connected to the tubular body 58 of the measuring electrode 4 by being inserted into the inflow hole 63 of the prime body 23. From the proximal end of the inflow pipe 12a, . The distal end of the inflow pipe 12a and the tube 58 of the measuring electrode 4 are connected to be closely contacted by an adhesive or the like so that the measuring liquid 9 does not leak but flows into the measuring electrode 4. [

The outflow pipe 12b has its proximal end inserted into the outflow hole 65 of the prime body 23 and connected to the second flow path 64 of the comparative electrode 6, Is discharged. The proximal end of the outflow pipe 12b and the second flow path 64 of the comparison electrode 6 are connected to each other so as to be closely contacted by an adhesive or the like so that the measurement liquid 9 is discharged from the second flow path 64 without leaking .

The distribution pump 10 is disposed between a predetermined position of the inflow pipe 12a or the outflow pipe 12b, for example, between the proximal end and the distal end of the outflow pipe 12b. The measuring liquid 9 flows through the inlet pipe 12a, the measuring electrode 4 and the comparing electrode 6 in this order by the operation of the circulating pump 10 and flows through the outlet pipe 12b, (Not shown).

Next, the internal liquid replenishing mechanism 5 will be described with reference to Figs. 1 and 2. Fig. The internal liquid replenishing mechanism 5 includes a container 16 in which the second internal liquid 15 is stored and a container 16 in which the comparative electrode 6 is connected and the second internal liquid 15 And a replenishment pump 18 which is disposed at a predetermined place of the replenishment pipe 20 and distributes the second inner liquid 15. The replenishment pipe 20 is provided in the replenishment pipe 20, The replenishment tube 20 has its proximal end connected to the container 16 and its distal end inserted into the inflow hole 67 of the prime body 23 and connected to the replenishment port 17. The tip end of the replenishing tube 20 and the replenishing port 17 of the comparison electrode 6 are brought into close contact with each other by an adhesive or the like so that the second inner liquid 15 does not leak but flows into the second inner liquid chamber 36 Respectively. On the other hand, an O-ring or the like may be provided between the replenishing tube 20 and the replenishing port 17 in order to improve the adhesion.

The replenishment pump 18 is disposed between the proximal end and the distal end of the replenishment pipe 20. The operation of the replenishment pump 18 causes the second internal liquid 15 to flow from the container 16 And the tube 20 is made to flow through the replenishment port 17 and replenished to the comparative electrode 6.

Next, the information processing and control mechanism 19 will be described with reference to Figs. 1 and 2. Fig. The information processing and control mechanism 19 operates the potentiometer 26 for calculating the pH value of the measurement liquid 9 measured by the electrode device 7 and the circulation pump 10 and the replenishment pump 18 And a control device 29 including a computer and a display for processing information obtained from the potentiometer 26 and outputting an operation signal or the like to the driver circuit 34 . In the present embodiment, the control device 29 is arranged outside the casing 2. [ On the other hand, the information processing / control mechanism 19 itself may be disposed outside the casing 2. [

The potentiometer 26 is connected to the inner electrode M of the measuring electrode 4 and the inner electrode R of the comparing electrode 6 in the electrode device 7 through the above- And are electrically connected by the inner pole (M) wiring 22 and the inner pole (R) wiring 24. Thereby, the potential difference between the electrodes is measured by the potentiometer 26 based on the respective potentials detected by the inner and outer poles (M) and (R). The potentiometer 26 is electrically connected to the control device 29 via the external connection terminal 28. The control device 29 causes the computer to measure the output value of the potentiometer 26 9), and displays the value on the display. The calculated pH value is stored in a storage medium of a computer so that it can be displayed when necessary.

The driver circuit 34 is electrically connected to the circulation pump 10 and the replenishing pump 18 through the wirings 30 and 32 and the driver circuit 34 is connected to the external connection terminals 28 And is electrically connected to the control device 29. The driver circuit 34 controls the operation and stoppage of the circulation pump 10 and the replenishing pump 18 based on a signal from the computer of the control device 29 so that the measurement liquid 9 is supplied to the electrode device 7 ), And the like. The replenishment amount of the second internal liquid 15 and the replenishment timing are controlled so that the measurement system 100 can continuously operate for several months, for example, for about 4 to 8 months.

Next, the measurement procedure of the pH measurement of the measurement liquid 9 using the measurement system 100 will be described with reference to Fig. The line P1 indicates on and off of the operation of the flow pump 10, and the convex portion indicates the ON and the concave portion indicates OFF. P2 similarly show the ON / OFF state of the operation of the supplementary pump 18. The pH indicates a state in which convex portions are subjected to pH measurement and a concave portion is not in the state.

First, after the measurement electrode 4 and the comparison electrode 6 are calibrated (not shown), measurement is started. First, measurement 1 will be described. In the measurement 1, the information processing / control mechanism 19 operates the circulation pump 10 (P1) of the internal liquid replenishing mechanism 5 for a predetermined time, and measures the flow rate of the liquid in the inflow pipe 12a and the outflow pipe 12b The liquid 9 flows into the measuring electrode 4 and the comparing electrode 6 while allowing the liquid 9 to flow. The amount of the measurement liquid 9 introduced at this time is, for example, several hundreds of microliters. After the measurement liquid 9 flows into the measurement electrode 4 and the comparison electrode 6, the flow pump 10 is once stopped. Measure the pH at this time.

In this manner, the pH measurement is performed by repeating the measurement of n times of times, for example, about 50 to 200 times in succession, with the measurement of the operation of the circulation pump 10, the stop, and the pH measurement in measurement 1 as one measurement. After the pH measurement, the flow pump 10 is stopped by the information processing / control mechanism 19, the replenishment pumps 18 and P2 are operated for a predetermined time, and the second internal liquid such as a KCl solution (15) is supplemented to the second internal liquid chamber (36) of the comparison electrode (6) by a predetermined amount. The replenishing amount at this time is such that the amount by which the measuring liquid 9 flows in from the liquid-storing portion 40 and the portion where the concentration of the second inner liquid 15 becomes thin can be replenished in the comparative electrode 6 , For example, several tens of microliters of internal liquid is replenished.

The n times of measurement and the replenishment of the second internal liquid 15 are set as one measurement routine and the measurement routine is repeated so that the second internal liquid 15 is periodically replenished and the desired number of measurement routines are terminated After that, the pH measurement is terminated.

Since the measuring electrode 4 is constructed as described above, the potential measurement can be performed by letting the measuring liquid 9 flow into the capillary tube 58, thereby reducing the amount of the measuring liquid 9 used for the measurement . This makes it possible to reduce the amount of the chemical liquid to be discarded after the measurement. In particular, when the circulation pump 9 is stopped to stop the flow of the measurement liquid 9 to measure the potential, the amount of the chemical liquid to be used can be further reduced.

Even when the temperature of the measurement liquid 9 is high, for example, about 50 캜, the temperature of the measurement liquid 9 is lowered while flowing in the tubular body 58, so that even if the circulation pump 10 is stopped It is possible to prevent unevenness of the measurement potential due to convection since the convection in the tubular body does not occur and the precision of the potential measurement can be improved. Since the flow pump 10 is stopped, pH measurement is performed on the measurement electrode 4 and the comparison electrode 6 in a state where the flow of the measurement liquid is stopped. As a result, Can be eliminated.

In the present embodiment, the tube 58 is located above the upper end of the inner pole M and is arranged to pass through a certain section of the first inner liquid chamber 52, Bubbles generated around the first inner liquid chamber 52 and the second inner liquid chamber 52 do not adhere to the tubular body 58 but are collected at the upper portion of the first inner liquid chamber 52. This makes it possible to prevent the measurement accuracy from being lowered by the bubbles. On the other hand, in the present embodiment, the upper end of the first inner liquid chamber 52 is formed into a conical shape in which the cross-sectional shape is reduced as it goes upward, but the present invention is not limited to this, Hemispherical shape, or the like, and a space in which air bubbles gather above the tubular body 58 may be formed.

Further, since the response glass of the tube 58 contains a predetermined amount of scandium, it is difficult to be eroded even when the chemical solution to be measured has a hydrofluoric acid resistance and the strongly acidic substance including hydrofluoric acid is used.

The bubble 47 contained in the measurement liquid 9 remains in the opening 45 because the comparison electrode 6 is configured as described above. Therefore, the interconnecting member 41 is not covered by the air bubbles, so that the measurement liquid 9 penetrates into the porous material or the fibers of the interconnecting member 41 and comes into contact with the second internal liquid 15, ) And the second internal liquid 15 are maintained, the potential of the measurement liquid 9 can be stably measured.

It is more preferable that the interconnecting member 41 has chemical resistance. The conductive member 41 can be used for a long period of time without causing corrosion or the like even if the measuring liquid 9 has a strongly acidic or strongly alkaline solution.

The upper end of the interconnecting member 41 may be formed so as to be substantially flush with the opening 45 or to protrude from the opening 45 toward the second flow path 64, The bubble contained in the measurement liquid 9 can be prevented from covering the conduction member 41 because it is disposed at a position lower than the opening 45 to the extent that the measurement liquid 9 does not stay. Therefore, since the upper end portion of the interconnecting member 41 can make contact with the measurement liquid 9, the measurement liquid 9 and the second internal liquid 15 are electrically connected, and the potential measurement can be performed.

Since the interconnecting member 41 is provided extending in the direction of the inner pole R, even when bubbles are gathered in the whole of the liquid-crystal part 40, the lower end of the interconnecting member 41 becomes the second inner liquid (15) so that conduction between the measurement liquid (9) and the second internal liquid (15) can be maintained.

When the lower end portion of the interconnecting member 41 is disposed below the upper end of the inner electrode R, the second inner liquid R flows from the bottom of the second inner liquid chamber 36 at the time of assembling the comparative electrode 6, The second inner liquid 15 which transfers the inner electrode R to the upper end thereof reaches the lower end of the interconnecting member 41 and then the interconnecting member 41 There is a possibility that a wall of the second inner liquid 15 is formed between the inner electrode R and the interconnecting member 41 and the inner wall surface by coming to the inner wall surface of the second inner liquid chamber 36 . In such a case, there is a case where air is collected in the inside of the wall, and the second internal liquid 15 can not be filled in that part.

However, if the interconnecting member 41 is disposed above the upper end of the inner pole R and between the upper end 43 of the second inner liquid chamber 36 and the predetermined distance L1, A wall of the inner liquid 15 does not occur and the second inner liquid 15 can be filled evenly in the second inner liquid chamber 36. [

The lower end of the interconnecting member 41 may be located below the upper end of the inner pole R. For example, the interconnecting member 41 may be located on the inner wall surface of the second inner liquid chamber 36 And the conductive member 41 may be located at a position away from the upper end of the inner pole R. [ With such a configuration, there is no possibility that a wall of the second inner liquid 15 is formed between the inner electrode R and the interconnecting member 41 and the inner wall surface, The liquid 15 can be reliably filled.

The second inner liquid 15 is replenished from the replenishment port 17 located below the upper end of the inner electrode R and the second inner liquid 15 is replenished to the vicinity of the inner electrode R The liquid can be replaced with the second inner liquid 15, and measurement accuracy can be maintained. In this case, since the measurement liquid 9 is introduced from the liquid 40 and the second internal liquid 15 is displaced by pushing up the thinned portion, the amount of the second internal liquid 15 15) can be supplemented, and the amount to be supplemented can be saved and reduced.

The position of the replenishing port 17 may be changed as appropriate, but the replenishing port 17 may be located further downward, that is, the lower end of the second inner liquid chamber 36. In this case, Even if the specific gravity of the measurement liquid 9 is smaller than the measurement liquid 9, the supplemented second internal liquid 15 does not flow out from the liquid-phase portion 40, It is possible to reliably replace the liquid around the inner electrode R and to save the amount of the second internal liquid 15 to be replenished.

When the specific gravity of the second internal liquid 15 is larger than the measurement liquid 9, the replenishing opening 17 may be located above the upper end of the internal electrode R. In this case, since the specific gravity of the second inner liquid 15 is larger than that of the measurement liquid 9, the second inner liquid 15 flows out from the liquid-storing portion 40 to the measurement liquid 9 immediately after the second inner liquid 15 is replenished And remains around the inner electrode R by its own weight so that the concentration of the second inner liquid 15 around the inner electrode R can be maintained. The second inner liquid 15 having a specific gravity larger than that of the measuring liquid 9 is replenished so that the measuring liquid 9 flows from the liquid-storing portion 40 to more reliably push the thinned portion of the second inner liquid 15 So that the liquid around the inner electrode (R) can be replaced with the second inner liquid (15). The amount of the second internal liquid 15 to be replenished can be an amount corresponding to the portion where the measurement liquid 9 flows in and becomes thinner, so that the replenishing amount of the second internal liquid 15 can be saved and reduced.

Since the inner pole R is arranged so as to extend upward from the lower end of the second inner liquid chamber 36, the replenishment pump 18 of the inner liquid replenishing mechanism 5, Even if the internal liquid 15 is intermittently replenished, the second internal liquid 15 can be sufficiently replaced before the upper portion of the second internal liquid chamber 36 becomes thinner than the inner electrode R, (R) can be maintained. As described above, since the second inner liquid 15 can be supplemented intermittently, the amount of the second inner liquid 15 to be supplemented can be reduced as compared with the case of continuously replenishing during the pH measurement, The measuring system 100 can be continuously operated without supplementing the second internal liquid 15 for about 4 to 8 months.

On the other hand, the replenishing pump 18 is operated so that the second internal liquid 15 flows in a minute amount without stopping the replenishment pump 18 completely, and the amount of the amount of the measurement liquid 9 flowing into the thinned portion 2 replenishment pump 18 may be operated to replenish internal liquid 15, but as described above, replenishment pump 18 preferably stops during pH measurement.

Since the sectional area at the predetermined distance L1 from the upper end 43 of the second inner liquid chamber 36 is smaller than the sectional area below the position at the predetermined distance L1, The amount of the portion in which the measurement liquid 9 flows from the liquid portion 40 and the second internal liquid 15 becomes thinner can be further reduced. Therefore, the amount of the portion to be substituted for the second inner liquid 15 becomes small, and thereby the amount of the second inner liquid 15 to be supplemented can be further reduced.

The predetermined distance L1 is variously changed depending on the measurement conditions. For example, after the pH measurement is performed for a predetermined time, the volume of the measurement liquid 9 is set to V2 and the volume of the second internal liquid 15 36 from the upper end portion 43 is L2. When the capacity to the predetermined distance L1 of the second internal liquid chamber 36 is V1, V1 and L1 are configured such that the relationship of V2 <V1 and L2 <L1 is established.

The replenishment amount of the second internal liquid 15 to be supplemented is determined based on the predetermined distance L1 thus determined and the capacity V1 thereof. In this case, the replenishment amount is V3, L2 &lt; L3 &lt; L1, and the portion thinned by the measurement liquid 9 is referred to as a second inner liquid (L3 &lt; L3) 15). &Lt; / RTI &gt;

Assuming that the replenishment amount V3 satisfies the relationship of V2 &lt; V1 &lt; V3, L2 <L1 <L3 and the portion thinned by the measurement liquid 9 is sufficient for the second inner liquid 15 . That is, when the measurement liquid 9 diffuses between the upper end portion 43 of the second inner liquid chamber 36 and the predetermined distance L1 and the second inner liquid 15 becomes thinner, A larger amount of the second inner liquid 15 is replenished so that the thinned portion can be reliably extruded from the liquid-absorbing portion 40 and replaced with the second inner liquid 15.

On the other hand, the relationship between the capacity V2 of the thinned portion and the replenishment amount V3 of the second internal liquid 15 may be such that at least V2 &lt; V3 is established.

Next, the electrode device 307 will be described as another embodiment of the electrode device 7 with reference to Fig. On the other hand, the code shown in Fig. 6 is the same as Fig. 2, and shows the same or corresponding configuration as the above embodiment.

The electrode device 307 is provided with a measuring electrode 304 and a comparison electrode 306 as shown in Fig.

The measuring electrode 304 includes a first body 354a having a first inner liquid chamber 352 in which the first inner liquid 350 is received and a second body 354b disposed apart from the first body 354a, And a connection body 354c connecting the first body 354a and the sub body 354b. The measuring electrode 304 is provided with an inner electrode M attached to extend from the lower portion of the first body 354a so that the first inner liquid chamber 352 extends upward. A body 354 of the measuring electrode 304 is formed from the first body 354a, the sub body 354b and the connecting body 354c. These bodies are formed of the same material as the first body 54. Like the first body 54, the first body 354a includes a main member 354d and a cover 354e. The first body 354a has a first inner liquid chamber 352 Is formed.

The upper end of one side of the first body 354a and the upper end of one side of the sub-body 354b are connected to each other by a substantially rectangular parallelepiped connection body 354c So that they are spaced apart from each other by a predetermined distance from the first body 354a. A space S1 is formed between the first body 354a and the sub body 354b which are separated from each other by opening below the first body 354a and the sub body 354b. In this embodiment, a sub-body 354b is similarly connected to the connection body 354c on the other side surface of the first body 354a, and is disposed apart from the first body 354a. Since each body is connected as described above, the measuring electrode 304 has the sub body 354b with the connecting body 354c therebetween on both sides around the first body 354a, And is formed in a substantially T shape.

A female screw hole 388 is formed in the sub-body 354b as a connection port with the comparative electrode 306. A female screw hole 388 is formed in the female screw hole 388, A male screw member 386 is disposed. Further, the female screw hole 388 and the space S1 are communicated with each other by the communication hole 380.

In this embodiment, the measuring electrode 304 is provided with a tube 358 through which the measurement liquid 9 flows.

This tube 358 is entirely formed of a response glass responsive to hydrogen ions, and forms a first flow path 362 through which the measurement liquid 9 flows. The downstream side of the first flow path 362 is the output end side of the tubular body 358 and the upstream side of the first flow path 362 is the input end side of the tubular body 358. [ The tubular body 358 has the same material and shape as the tubular body 58. Similarly to the case where the tube 58 is disposed on the first body 54, the tube 358 is disposed on the first body 354a.

The output end side of the tubular body 358 protrudes from the first body 354a and is inserted into the communication hole 380 of the sub body 354b. As a result, a part of the tubular body 358 is put in a space S1 formed between the first body 354a and the sub body 354b, and this part of the tubular body 358 is in the space S1. .

In the present embodiment, the input end side of the tubular body 358 also protrudes from the first body 354a, and the input end side thereof is a sub-body disposed apart from the other side surface of the first body 354a. And is inserted into the communication hole 380 formed in the communication hole 354b.

On the other hand, the tubular body 358 may use a response glass for a part of the tubular body 358 to be immersed in the first inner liquid 350.

The structure of the comparative electrode 306 is the same as that of the comparative electrode 6 in the above embodiment.

Next, a specific configuration of the electrode device 307 will be described. The electrode device 307 is configured such that the tube 358 and the second flow path 64 of the comparison electrode 306 are connected by the connecting pipe 382 and the measuring liquid 9 is connected to the measuring electrode 304 to the comparative electrode 306. [0053]

Concretely, the other end side of the connection pipe 382 is fitted outside from the output end side of the tubular body 358, and one end side of the connection pipe 382 is connected to the second flow path 64 by adhesive or the like, A flow path through which the measurement liquid 9 flows is formed. Further, an annular member 390 for pressing and attaching the periphery of the connecting pipe 382 is formed at a portion where the connecting pipe 382 is fitted. More specifically, the annular member 390 is an annular member such as a ferule having a tapered surface, and by screwing the male screw member 386 to the female screw hole 388, the male screw member 386 So that the portion of the connecting tube 382 which is fitted outside of the connecting tube 382 is pressed by the ferrule and the connecting tube 382 is fixed so as not to come off from the tube body 358. [

The distal end of the inflow pipe 12a is connected to the input end of the tubular body 358 and the measurement liquid 9 is introduced into the tubular body 358 from the inflow pipe 12a. For example, the distal end portion of the inflow pipe 12a is fitted outside to the input end side of the tubular body 358, and the fixing member is provided at the portion as described above, so that the inflow tube 12a is fixed .

The tubular body 358 is fixed by an adhesive or the like to the first inner liquid chamber 352 and the first inner liquid chamber 350 is fixed to the first inner liquid chamber 352, As shown in Fig.

Even if the first internal liquid 350 leaks from aging deterioration or the like from the portion of the body 358 passing through the first body 354a because the electrode device 307 is configured as described above The transfer of the first internal liquid 350 to the comparative electrode 306 is blocked in the space exposed area formed on the output end side of the tubular body 358. As a result, It is possible to reliably prevent the first inner liquid 350 of the measuring electrode 304 from being mixed into the second flow path 64. The larger the space-exposed area, the more surely the transmission of the first inner liquid 350 to the comparison electrode 306 can be blocked more surely, so that the predetermined length of the protruding part is preferably longer.

In addition, since the measuring electrode 304 further includes the sub-body 354b in the first body 354a, the protruding portion of the body 358 can be held by the sub-body 354b.

When the sub body 354b is connected to the first body 354a by the connection body 354c, the first body 354a, the sub body 354b, and the connection body 354c are integrally formed . Therefore, the protruding portion of the tube 358 can be more stably maintained in the sub-body 354b, and it is possible to prevent the tube 358 from being folded or cracked due to the unfavorable bending force acting on the tube 358. [

The distance between the first body 354a and the sub-body 354b is determined by the width of the connecting body 354c connecting them. However, by widening the width of the connecting body 354c, the distance between the first body 354a and the sub- This makes it possible to more reliably block the first inner liquid 350 into the comparison electrode 306. For example, in the case where it is assumed that the leakage of the first inner liquid 350 is increased, it is preferable to do so.

Since the female-threaded hole 388 as the connection port for the second flow path 64 of the comparison electrode 306 is formed on the side of the sub-body 354b which is in contact with the comparison electrode 306, It is possible to securely supply the measuring liquid 9 to the second flow path 64 by firmly connecting the tubular body 385 and the connecting pipe 382.

Also, the second sub-body and the second connection body may be provided on the comparison electrode 306 so that the projecting portion of the tube 358 can be held. Specifically, on the side of the measuring electrode 304 side of the comparison electrode 306, a second sub body of the block body is formed with the second connection body interposed therebetween. As such, the second sub-body is spaced apart from the second body 42, thereby forming the same space as the space. By this second sub-body, the tube 358 protruding from the first body 354a is held, and a part of the tube 358 is configured to span the space.

In this case, since the second sub body is formed in the second body 42 of the comparison electrode 306 with the second connection body interposed therebetween, the tube body 358 can be held without being damaged. In addition, since the tube 358 is partly covered with the space formed by the second body 42 and the second connection body, a space-exposed region is formed in the tube 358, and the first inner liquid 350 To the comparison electrode 306 can be blocked.

Next, the electrode device 407 will be described as still another embodiment of the electrode device 7 with reference to Fig.

The electrode device 407 includes a measuring electrode 404 and a comparison electrode 406 as shown in Fig.

The tube body 458 of the electrode device 407 is formed by connecting a plurality of tubular elements and all of the tubular body 358 of the electrode device 307 is formed of a reaction glass And the resilient tube 458b made of resin are constituted as tubular elements. That is, a part of the tubular body 458 is composed of a response glass. The output end side (one end side of the elastic tube 458b) of the tubular body 458 is connected to the second flow path 464 of the comparison electrode 406 and the measurement liquid 9 is supplied from the measurement electrode 404, (406). A second internal liquid chamber 436 in which the second internal liquid 415 is accommodated is formed in the second body 442 of the comparison electrode 406, And is in contact with the measurement liquid 9 flowing through the second flow path 464 through the lock portion 440.

Concretely, the other end of the elastic tube 458b is fitted to one end of the response glass tube 458a from the outside, and an annular fixing member 490 Is formed. More specifically, the fixing member 490 is, for example, a conical ferrule having a tapered surface, and a male screw member 486 is formed so as to contact the tapered surface with a female screw hole 484 formed in the first body 454a. (488). Thereby, the male screw member 488 is pressed into the ferrule, and the portion of the elastic tube 458b which is fitted outside is pressed by the ferrule, and the response glass tube 458a and the elastic tube 458b are connected .

Since the elastic tube 458b has an elastic force, when pressed by the ferrule, the elastic tube 458b comes into close contact with the response glass tube 458a formed of a rigid response glass, The tube 458b is connected in a liquid-tight manner.

The output end side of the tubular body 458 (one end side of the elastic tube 458b) is likewise connected to the second flow path 464 by using the fixing member 490 or the like.

Since the measurement electrode 404 and the comparison electrode 406 are separated from each other and the space S2 is formed therebetween, the measurement electrode 404 and the comparison electrode 406 are connected to the measurement system 300 because the elastic tube 458b is smooth. The elastic tube 458b can absorb the difference even if the position of the electrode unit 407 is shifted, so that the electrode unit 407 can be easily assembled.

The first internal liquid 450 accommodated in the first internal liquid chamber 452 is discharged from the first flow path 450 which is the flow path of the measurement liquid 9, It can be prevented that it is mixed with the electrode 462 and the precision of the potential measurement can be maintained.

For example, one end of the response glass tube 458a protruding from the first body 454a and the other end of the elastic tube 458b are closely contacted with an adhesive or the like without using the fixing member 490 . The outlet end of the tubular body 458 may also be connected to the second flow path 464 by adhesive or the like.

On the other hand, instead of the elastic tube 458b, a rigid pipe-shaped pipe may be connected to the response glass tube 458a to form the pipe body 458 to form the space S2.

The measuring electrode 404 or the comparing electrode 406 may be provided with a sub body and a connecting body similar to the measuring electrode 304 so as to form the space S2 to hold the tube 458 .

Next, the electrode device 507 will be described as still another embodiment of the electrode device 7 with reference to Fig. 6 and 7 are the same as or corresponding to those of the above embodiment.

The electrode device 507 includes a measuring electrode 504 and a comparison electrode 506 as shown in Fig.

The measurement electrode 504 has the same configuration as the measurement electrode 304, and the measurement electrode 304 is arranged upside down. Therefore, detailed description of the configuration of the measuring electrode 504 is omitted.

The comparison electrode 506 has the same configuration as the comparison electrode 406. Therefore, detailed description of the configuration of the comparison electrode 506 is omitted.

Next, the electrode device 507 will be described. In this electrode device 507, the measurement electrode 504 and the comparison electrode 506 are disposed apart from each other. However, like the electrode device 307 described above, the tube 358 and the second electrode 506 of the comparison electrode 506, The reference electrode 64 is connected by the connection pipe 382 and the measurement liquid 9 is supplied from the measurement electrode 504 to the comparison electrode 506. [ Since the connecting structure of the measuring electrode 504 and the comparing electrode 506 in the connecting pipe 382 is the same as that of the measuring electrode 404 and the comparing electrode 406, do.

The bubbles generated around the tubular body 358 disposed below the first internal liquid chamber 352 of the measuring electrode 504 are discharged from the first internal liquid chamber 352 by the pH measurement because the electrode apparatus 507 is configured as described above. 352 (in the direction of the cover 354e). Thereby, the bubble does not adhere to the tube 358, and it is possible to prevent the measurement accuracy from being lowered by the bubble.

&Lt; Second Embodiment &gt;

Next, the comparative electrode system incorporating the comparative electrode of the first embodiment will be described, but the description will be made by using different reference numerals from those of the first embodiment.

9 and 10, the comparison electrode system 1z according to the second embodiment includes a measurement liquid pipe 2z as a measurement liquid accommodation portion through which the measurement liquid 9z flows, A comparison electrode accommodating portion 3z having an inner electrode 3za immersed in the inner liquid and a connection pipe 4z connecting the measurement liquid pipe 2z and the comparison electrode accommodating portion 3z. On the other hand, in the present embodiment, the part of the measurement liquid pipe 2z, the comparison electrode accommodation part 3z and the connection pipe 4z is housed inside the transparent block member 6z.

The measurement liquid pipe 2z is a flow path through which the measurement liquid flows and extends horizontally from one side to the other side of the block body 6z. In the present embodiment, connection joints 7z for connecting to, for example, tanks or glass electrodes to which a measuring liquid is connected are provided at both ends thereof.

The measurement liquid is, for example, a liquid or the like containing mostly a solvent such as a cleaning liquid for semiconductor, and has a specific gravity of about 1.19 g / cm 3. On the other hand, the measurement liquid is not limited to this, and any sample can be used for electrochemical measurement.

The comparison electrode accommodating portion 3z includes an accommodating container (inner liquid chamber) 3zb having a substantially cylindrical shape and an inner electrode 3za made of, for example, AgCl or the like disposed so as to rise in the interior of the accommodation container 3zb, A tank 3zc that is stored in the storage container 3b and stores the internal liquid immersed in the internal electrode 3za, the internal liquid, and the storage container 3zb and the tank 3zc, A supply pipe 3zd for supplying the inner liquid to the inner pipe 3zb and a valve 3ze for opening and closing the supply pipe 3zd. The receiving container 3zb is disposed so as to extend from the upper surface to the lower surface of the block member 6z.

The internal solution is, for example, 3.3 moles of KCl solution or the like, having a specific gravity of 1.17 g / cm 3 and having a specific gravity smaller than that of the solution to be measured. On the other hand, the electrode 3za and the internal solution described above are not limited to these, and can be appropriately changed in accordance with the sample to be subjected to the electrochemical measurement.

10, the connecting pipe 4z connects the measuring liquid pipe 2z and the comparative electrode receiving portion 3z to each other. In the present embodiment, the bottom pipe portion 4za and the upper pipe portion A first communicating pipe portion 4zb extending upward from one end of the bottom pipe portion 4za and communicating with the measuring liquid pipe 2z and extending upward from the other end of the bottom pipe portion 4za, A second communicating pipe portion 4zc (which extends downward from one end of the upper pipe portion 4zd and communicates with the bottom pipe portion 4za) communicating with the upper pipe portion 4zd, And a third communicating tube 4ze extending downward from the other end of the first communicating tube 4zd and communicating with the accommodating container (inner liquid chamber) 3zb.

The bottom pipe portion 4za, a portion of the first communication pipe portion 4zb, the second communicating pipe portion 4zc, the upper pipe portion 4zd, and the third communicating pipe 4ze are disposed outside the block member 6z And is composed of a tube. On the other hand, the other part of the first communication pipe portion 4zb is accommodated in the block member 6z.

The other part of the first communication piping part 4zb (that is, the upper part of the first communication piping part 4zb) is connected to the measurement liquid piping 2z, and the connection part is structured by the liquid lock part 45z ). In the upper portion of the first communication pipe portion 4zb, a conduction member 41z is formed similarly to the first embodiment.

The operation of the comparative electrode system 1z constructed as described above will be described below.

First, the valve 3ze provided in the comparison electrode accommodating portion 3z is opened, and when the internal liquid is supplied to the accommodating container 3zb, the supplied internal liquid is filled in the accommodating container 3zb and the connection pipe 4z And reaches the connection portion between the measurement liquid pipe 2z and the connection pipe 4z. Then, the valve 3ze is closed to stop the supply of the internal liquid. This process is referred to as a measurement start process for the following description.

Then, the measurement liquid is caused to flow through the measurement liquid pipe 2z. When the specific gravity of the measurement liquid is heavier than the internal liquid, the measurement liquid is introduced from the structured liquid lock portion 45z and pressed from the pipeline 2z for measurement liquid to the first communication piping portion 4zb and the bottom Both ends of the bottom pipe portion 4za are communicated with the first communicating pipe portion 4zb and the second communicating pipe portion 4zc which are extended to the upper side so that the bottom pipe portion 4za is connected to the bottom pipe portion 4za The outflow is stopped. Then, at this stopped position, a substantial droplet portion in contact with the measurement liquid and the inner liquid is generated. By forming this liquid portion, the inner electrode 3za is electrically connected to the measurement liquid, thereby exerting a function as a comparison electrode. This process is referred to as a measurement process for the following description.

Next, the comparison electrode system 1z is calibrated.

The valve 3z is opened to allow the internal liquid to flow from the container 3zb to the measurement liquid pipe 2z via the connection pipe 4z and the connection pipe 4z ) Or the measuring liquid for measurement liquid 2z. This process is referred to as a calibration preparation process for the following description. In this calibration preparation step, the measurement liquid remaining in the connection pipe 4z can be removed, and deterioration of measurement accuracy can be prevented.

When the predetermined time has elapsed, the calibration solution is caused to flow through the measurement liquid pipe 2z in a state where the valve 3ze is closed and the supply of the internal liquid is stopped. This process is referred to as a calibration process for the following description. At this time, since the connection pipe 4z is connected to the lower portion of the measurement liquid pipe 2z in the vertical direction, the calibrator solution having a specific gravity smaller than that of the internal liquid does not flow into the connection pipe 4z, It is possible to prevent the third electrode 3za from being corroded.

Finally, after stopping the flow of the calibration liquid, the valve 3ze is opened to flow the internal liquid, and the flow returns to the measurement start process. In the series of operations described above, the valve 3ze is opened in the measurement start process and the calibration preparation process.

According to the comparative electrode system 1z of the second embodiment configured as described above, the following effects are obtained.

That is, when the specific gravity of the liquid to be measured is larger than the internal liquid, the liquid to be measured is pushed into the connection pipe 4z connected to the liquid pipe 2z for measuring solution liquid in the vertical direction. However, since the connection pipe 4z includes the bottom pipe portion 4za and the first communicating pipe portion 4zb and the second communicating pipe portion 4zc that extend upward from both ends of the bottom pipe portion 4za, The inflow of the measurement liquid is stopped at the bottom piping 4za. Therefore, it is possible to prevent the measurement liquid from intruding into the interior of the accommodation container (internal liquid chamber) 3zb and to prevent the internal electrode 3za contained in the accommodation container (internal liquid chamber) 3z from being corroded by the measurement liquid have.

In order to prevent the measurement liquid from intruding into the accommodation container (inner liquid chamber) 3zb, it is conceivable that the inner liquid continues to flow to prevent intrusion of the measurement liquid by the pressure of the inner liquid. It is possible to prevent the measurement liquid from intruding into the accommodation container (inner liquid chamber) 3zb without continuing to flow the inner liquid. Therefore, the valve 3ze can be intermittently operated to reduce the amount of the internal liquid to be used. Therefore, the size of the tank containing the internal liquid can be reduced, and the number of times the internal liquid is supplied to the tank can be reduced Can be reduced. In addition, since the internal liquid amount to be used is reduced, the cost can be suppressed.

In addition, since the comparison electrode system 1z is constituted by the block body 6z and the tube, the manufacturing can be simplified as compared with the case where all the components are provided in the block body 6z, Can be suppressed. In addition, since the block body 6z can be downsized as compared with the case where all the components are provided inside the block body 6z, the piping for measuring liquid, the comparative electrode receiving portion, the connecting pipe and the like are also downsized, Measurement can be performed even when the amount of liquid used is reduced.

&Lt; Third Embodiment &gt;

Next, the third embodiment of the present invention will be described, but the same parts as those of the second embodiment will be denoted by the same reference numerals, and a description thereof will be omitted.

11, the comparison electrode system 10z of the third embodiment differs from the first embodiment in the structure of the connection pipe 14z, and the connection pipe 14z of the third embodiment differs from the first embodiment in the structure of the connection pipe 14z, A first communicating pipe portion 14zb which extends upward from one end of the bottom pipe portion 14za and communicates with the measuring liquid pipe 2z and a second communicating pipe portion 14zb which extends upward from one end of the bottom pipe portion 14za, And the second communicating pipe portion 14zc extending downward from one end of the upper pipe portion 14zd and communicating with the bottom pipe portion 14za so as to communicate with the upper pipe portion 14z And a third communicating pipe portion 14ze extending downward from the other end of the upper pipe portion 14zd and communicating with the accommodation container (inner liquid chamber) 3zb.

The bottom pipe portion 14za, the first communicating pipe portion 14zb and the second communicating pipe portion 14zc are substantially U-shaped protruding downward. The upper pipe portion 14zd, the second communicating pipe portion 14zc And the third communicating tube portion 14ze are substantially U-shaped projecting upward. The bottom pipe portion 14za, the first communicating pipe portion 14zb, the second communicating pipe portion 14zc, the upper pipe portion 14zd, and the third communicating pipe portion 14ze are all made of tubes.

The connecting portion between the upper portion of the first communicating pipe portion 14zb and the measuring liquid pipe 2z becomes a structured liquid-storing portion 45z. In the upper portion of the first communication pipe portion 14zb, a conduction member 41z is provided similarly to the first embodiment.

When the specific gravity of the internal liquid is smaller than the liquid to be measured, the liquid to be measured flows from the structured liquid lock portion 45z and is pushed to pressurize the internal liquid, and the connection pipe 4z Lt; / RTI &gt; However, since the first communicating tube portion 14zb and the second communicating tube portion 14zc, which communicate with both ends of the bottom pipe portion 14za, are extended upward, the penetration of the measurement liquid into the bottom pipe portion 14za is stopped. At this position, a substantial liquid-circulating portion in which the measuring liquid and the inner liquid come into contact is formed.

In the comparative electrode system 10z of the second embodiment thus provided as well, the bottom pipe portion 14za, the first communicating pipe portion 14zb extending upward from both ends of the bottom pipe portion 14za, (Inner liquid chamber) 3zb to prevent the inflow of the liquid to be measured to the inside of the container (inner liquid chamber) 3zb by stopping the inflow of the liquid to be measured at the bottom pipe portion 14za, It is possible to prevent corrosion of the inner electrode accommodated in the measurement liquid.

&Lt; Fourth Embodiment &

Next, the fourth embodiment of the present invention will be described, but the same parts as those of the first embodiment and the second embodiment are denoted by the same reference numerals, and a description thereof will be omitted.

The comparative electrode system 20z according to the fourth embodiment is different from the comparative electrode system 20z according to the second and third embodiments and the configuration of the connection pipe 24z and the connection pipe 24z, ) Are different from each other.

That is, the connection pipe 24z is provided with an upper pipe portion 24za, a bottom pipe portion 24zd, and an upper pipe portion 24z, which extend downward from one end of the upper pipe portion 24za and communicate with the measurement liquid pipe 2z The first communicating pipe portion 24zb and the second communicating pipe portion 24zc extending downward from the other end of the upper pipe portion 24za and communicating with the bottom pipe portion 24zd And a third communicating pipe portion 24zd extending upward from the other end of the bottom pipe portion 24zd and communicating with the accommodation container (inner liquid chamber) 3zb, 24ze).

The upper pipe portion 24za, the first communicating pipe portion 24zb and the second communicating pipe portion 24zc are substantially U-shaped protruding upward and the bottom pipe portion 24zd, the second communicating pipe portion 24zc And the third communicating tube portion 24ze are substantially U-shaped protruding downward.

The connection pipe 24z is connected to the upper side of the measurement liquid pipe 2z in the vertical direction.

The connecting portion between the lower portion of the first communicating pipe portion 24zb and the measuring liquid pipe 2z serves as a structured liquid fastening portion 45z. In the lower portion of the first communication pipe portion 24zb, a conduction member 41z is provided similarly to the first embodiment.

When the specific gravity of the internal liquid is larger than the liquid to be measured, the liquid to be measured flows in from the structured liquid lock portion 45z and pushes up the internal liquid, and the connection pipe 4z connected to the upper part of the measurement liquid pipe 2z in the vertical direction Lt; / RTI &gt; However, since the first communicating pipe portion 24zb and the second communicating pipe portion 24zc, which communicate with both ends of the upper pipe portion 24za, extend downward, the inflow of the measurement liquid is stopped at the upper pipe portion 24za . At this position, a substantial liquid-circulating portion in which the measuring liquid and the inner liquid come into contact is formed.

Also in the comparative electrode system 20z of the fourth embodiment provided as described above, the first communicating pipe portion 24zb and the second communicating pipe portion 24z extending downward from both ends of the upper pipe portion 24za and the upper pipe portion 24za (Inner liquid chamber) 3zb to prevent the measurement liquid from intruding into the container (inner liquid chamber) 3zb by stopping the inflow of the liquid to be measured in the upper piping section 24za, Can be prevented from being corroded by the measurement liquid.

When the connection pipe 4z is provided above the measurement liquid pipe 2z in the vertical direction, the calibration liquid having a specific gravity smaller than that of the internal liquid is supplied from the measurement liquid pipe 2z to the connection pipe 4z, The flow of the calibrator solution in the upper piping section 24za is stopped by the above-described structure, so that it is also possible to prevent the calibrator solution from corroding the inner pole 3za.

On the other hand, the present invention is not limited to the first to fourth embodiments.

For example, in the second to fourth embodiments, the lyophobic member 8z may be provided inside the connection pipe 4z.

Specifically, as shown in Fig. 13, one end 8za of the lumen member 8z is provided in contact with the interconnecting member 41z, and the other end 8zb is provided in the inner liquid chamber 3zb . The one end 8za of the liquid retaining member 8z may be wound around the outer periphery of the lower end portion of the interconnecting member 41z or may have a structure in which the through hole formed in the interconnecting member 41z is penetrated. As the liquor member 8z, a material having resistance (chemical resistance) to the liquid to be measured and a material (for example, hollow fiber) capable of impregnating the liquid or internal liquid may be used.

Also in the second embodiment and the third embodiment, the measurement liquid flow path, the comparison electrode accommodation portion, the connection pipe, and the like may be provided inside the block body.

In addition, for example, when it is desired to simultaneously measure not only the hydrogen ion concentration but also the concentration of, for example, sodium ion, potassium ion or the like, And the measurement liquid flowing out from the measurement electrode may be merged to make the comparison electrodes common. Alternatively, a plurality of measurement electrodes may be provided in series so as to measure hydrogen ions, sodium ions, potassium ions, and the like in this order, and the comparison electrodes may be provided in series in succession to make the comparison electrodes common. In such a case, the measurement system can be made compact, and the concentration of a plurality of ions or the like can be measured simultaneously.

Industrial availability

According to the present invention, even in the case where bubbles are mixed in the measurement liquid, conduction between the internal liquid and the measurement liquid can be maintained in the liquid-liquid portion, and the potential measurement of the measurement liquid can be stably performed.

100: Measurement system
4, 304, 404, 504: measuring electrode
6, 306, 406, and 506:
7, 307, 407, 507: electrode device
10: Distribution pump
17: replenishment
18: Replacement pump
36: the second inner liquid chamber
40:
41: Conducting member
42: Second body
45: aperture
52: First inner liquid chamber
54: First body

Claims (10)

A body having an inner liquid chamber in which the inner liquid is contained and a liquid lock portion disposed in the inner liquid chamber so that the inner liquid and the measurement liquid to be measured are in contact with each other;
And an inner pole disposed in the inner liquid chamber,
Wherein the liquid crystal portion is formed by a conductive member formed of a porous or fibrous member and an opening adjacent to the conductive member. The method according to claim 1,
Wherein the conductive member is disposed such that the size of the opening is larger than the size of the fine hole of the conductive member. The method according to claim 1,
Wherein the end portion of the conductive member which is in contact with the measurement liquid is arranged so as to be substantially flush with the opening or to protrude from the opening toward the measurement liquid. The method according to claim 1,
Wherein the conductive member is provided so as to extend in the inner pole direction. The method according to claim 1,
Wherein the opening is disposed on the downstream side of the flow of the measurement liquid when the measurement liquid containing portion for containing the measurement liquid flows in one direction. The method according to claim 1,
Wherein the cross-sectional area of the inner liquid chamber from the upper end of the inner liquid chamber to a predetermined distance is smaller than the position of the inner liquid chamber at a predetermined distance from the upper end of the inner liquid chamber, The inner liquid chamber is formed so as to be smaller than the cross sectional area,
Wherein the conductive member is disposed between the upper end of the inner liquid chamber and the predetermined distance. The method according to claim 1,
A measuring liquid accommodating portion for accommodating the measuring liquid;
And a connection pipe for connecting the internal liquid chamber and the measurement liquid containing portion,
A first communicating pipe portion extending upward from one end of the bottom pipe portion and communicating with the measurement liquid accommodating portion; and a second communicating pipe portion extending upward from the other end of the bottom pipe portion, A second communicating tube portion communicating with the second communicating tube portion,
Wherein the connection pipe includes an upper pipe portion, a first communicating pipe portion extending downward from one end of the upper pipe portion and communicating with the measurement liquid accommodating portion, and a second communicating pipe portion extending downward from the other end of the upper pipe portion, And a second communicating tube portion communicating with the second communicating tube portion. 8. The method of claim 7,
Wherein the connection pipe is connected to the lower side of the vertical direction of the measurement liquid containing portion. 8. The method of claim 7,
And a liquefier member provided inside the connection pipe,
Wherein one end of the liquid-absorptive member is provided in contact with the conducting member, and the other end is provided in the inner liquid chamber. 10. The method of claim 9,
Wherein the liquid-absorptive member is a hollow fiber made of a material having chemical resistance.

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